The intrinsic properties of semiconducting oxides having nanostructured morphology are highly appealing for gas sensing. In this study, the fabrication of nanostructured WO₃ thin films with promising surface characteristics for hydrogen (H₂) gas sensing applications is accomplished. This is enabled by developing a chemical vapor deposition (CVD) process employing a new and volatile tungsten precursor bis(diisopropylamido)-bis(tert-butylimido)-tungsten(VI), [W(N^tBu)₂(NⁱPr₂)₂]. The as-grown nanostructured WO₃ layers are thoroughly analyzed. Particular attention is paid to stoichiometry, surface characteristics, and morphology, all of which strongly influence the gas-sensing potential of WO₃. Synchrotron-based ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS), X-ray photoelectron emission microscopy (XPEEM), low-energy electron microscopy (LEEM) and 4-point van der Pauw (vdP) technique made it possible to analyze the surface chemistry and structural uniformity with a spatially resolved insight into the chemical, electronic and electrical properties. The WO₃ layer is employed as a hydrogen (H₂) sensor within interdigitated mini-mobile sensor architecture capable of working using a standard computer's 5 V 1-wirebus connection. The sensor shows remarkable sensitivity toward H₂. The high, robust, and repeatable sensor response (S) is attributed to the homogenous distribution of the W⁵⁺ oxidation state and associated oxygen vacancies, as shown by synchrotron-based UPS, XPS, and XPEEM analysis.